EP0744432A1 - Particules solubles monodispersées d'organopolysiloxane - Google Patents

Particules solubles monodispersées d'organopolysiloxane Download PDF

Info

Publication number
EP0744432A1
EP0744432A1 EP96108218A EP96108218A EP0744432A1 EP 0744432 A1 EP0744432 A1 EP 0744432A1 EP 96108218 A EP96108218 A EP 96108218A EP 96108218 A EP96108218 A EP 96108218A EP 0744432 A1 EP0744432 A1 EP 0744432A1
Authority
EP
European Patent Office
Prior art keywords
units
general formula
weight
particles
organopolysiloxane particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96108218A
Other languages
German (de)
English (en)
Other versions
EP0744432B1 (fr
Inventor
Michael Dr. Geck
Bernward Dr. Deubzer
Manfred Prof. Dr. Schmidt
Frank Dr. Baumann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP0744432A1 publication Critical patent/EP0744432A1/fr
Application granted granted Critical
Publication of EP0744432B1 publication Critical patent/EP0744432B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

Definitions

  • the invention relates to a single molecule, crosslinked, monodisperse soluble organopolysiloxane particles which have an average diameter of 5 to 200 nm and their production.
  • US-A-4,424,297 describes organopolysiloxane particles in suspension which have an average diameter of 1 to 100 nm. After isolation as a powder, these particles are almost insoluble in all solvents, since the particles crosslink to form larger agglomerates via reactive groups still present on the surfaces, such as condensable alkoxy or silanol groups.
  • EP A-326 810 describes monodisperse organopolysiloxane particles which have an average diameter of 800 to 5000 nm. These particles are produced by slowly dropping methyltrialkoxysilane into aqueous, dilute ammonia or amine solution. The powder precipitated from the colloidal suspension is isolated and treated with a silylating agent. These particles are also almost insoluble in all solvents.
  • the object was to provide crosslinked organopolysiloxane particles consisting of a single molecule which have a monodisperse particle size distribution within a size range from 5 to 200 nm and which are at least 5% by weight soluble in a solvent.
  • the invention relates to crosslinked organopolysiloxane particles consisting of a single molecule, which have an average diameter of 5 to 200 nm, in which at least 80% of the particles have a diameter which deviates at most 30% from the average diameter and which are at least 5% by weight in a solvent .-% are soluble.
  • the organopolysiloxane particles typically have average molecular weights of at least 10 5 , in particular 5 ⁇ 10 5 to at most 10 10 , in particular 10 9 .
  • the average diameter of the organopolysiloxane particles is preferably at least 10 and at most 150 nm. At least 80% of the particles preferably have a diameter which deviates from the average diameter by at most 20%, in particular at most 10%.
  • the organopolysiloxane particles are preferably spherical microgels.
  • the organopolysiloxane particles are intramolecularly cross-linked, but have no intermolecular cross-linking between the organopolysiloxane particles.
  • the organopolysiloxane particles are therefore readily soluble in solvents.
  • the solvent in which the organopolysiloxane particles dissolve at least 5% by weight depends on the structure of the organopolysiloxane particles and in particular on the groups located on the surface of the organopolysiloxane particles. There is a suitable solvent for all organopolysiloxane particles.
  • solvents examples include water; Alcohols, such as methanol, ethanol, n-propanol, iso-propanol; Ethers such as dioxane, tetrahydrofuran, diethyl ether, diethylene glycol dimethyl ether; chlorinated hydrocarbons, such as dichloromethane, trichloromethane, carbon tetrachloride, 1,2-dichloroethane, trichlorethylene; Hydrocarbons, such as pentane, n-hexane, cyclohexane, hexane isomer mixtures, heptane, octane, mineral spirits, petroleum ether, benzene, toluene, xylenes; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Dimethylformamide, carbon disulfide and nitrobenzene, or mixtures of these solvents, and also monomers
  • the solubility of the organopolysiloxane particles can be determined, for example, at 20 ° C.
  • Toluene is particularly suitable as a solvent for organopolysiloxane particles with hydrocarbon radicals, tetrahydrofuran for organopolysiloxane particles with amino radicals and water for organopolysiloxane particles with sulfonate radicals.
  • organopolysiloxane particles with hydrocarbon residues are almost unlimited in toluene and soluble in liquid polydimethylsiloxane with a viscosity of 35 mPa ⁇ s at 25 ° C up to 15% by weight.
  • the organopolysiloxane particles are preferably soluble in a solvent which is selected from toluene, tetrahydrofuran and water to an extent of at least 10% by weight, in particular at least 15% by weight.
  • unsubstituted radicals R are alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl -, neo-pentyl, tert-pentyl radical, hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2,2,4- Trimethylpentyl, nonyl, such as the n-nonyl, decyl, such as the n-decyl, dodecyl, such as the n-dodecyl, octadecyl such as the n-octa
  • substituted hydrocarbon radicals as radical R are halogenated hydrocarbon radicals, such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3,3,3-trifluoropropyl and 5,5,5,4,4,3,3-heptafluoropentyl radical as well as the chlorophenyl, dichlorophenyl and trifluorotolyl radical; Mercaptoalkyl radicals, such as the 2-mercaptoethyl and 3-mercaptopropyl radical; Cyanoalkyl radicals, such as the 2-cyanoethyl and 3-cyanopropyl radicals; Aminoalkyl radicals, such as the 3-aminopropyl, N- (2-aminoethyl) -3-aminopropyl and N- (2-aminoethyl) -3-amino- (2-methyl) propyl radical; Aminoaryl radicals, such as the aminophenyl radical; quaternary ammonium residues,
  • the radical R is preferably unsubstituted and substituted C 1 -C 6 -alkyl radicals, hydrogen and the phenyl radical, in particular the methyl, phenyl, vinyl, allyl, methacryloxypropyl, 3-chloropropyl, 3 -Mercaptopropyl-, 3-aminopropyl and the (2-aminoethyl) -3-aminopropyl radical, hydrogen and quaternary ammonium radicals.
  • the interparticle condensation of the organopolysiloxane particles is prevented by saturating the remaining condensable groups after the first step with organosilicon compounds containing only monofunctional triorganosilyl groups.
  • no by-products such as hydrochloric acid or ammonia are formed in the hydrolysis or condensation reaction of the organosilicon compounds of the general formula (12), which substantially increase the ionic strength of the aqueous colloidal system.
  • Trimethylmethoxysilane, trimethylethoxysilane, hexamethyldisiloxane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, 1,1,3,3-tetramethyldisiloxane and mixtures thereof are particularly preferably used as organosilicon compounds of the general formula (12).
  • the organopolysiloxane particles can be isolated from the colloidal suspensions after the end of the second reaction step by known methods, for example by coagulating the latices by adding salt or by adding polar solvents.
  • organosilicon compounds of the general formula (13) are preferably used.
  • Particularly preferred organic silicon compounds of the general formula (13) in this third reaction step are trimethylchlorosilane, dimethylchlorosilane, vinyldimethylchlorosilane, Hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, or mixtures of disilazanes or chlorosilanes.
  • the amounts of compounds of the general formulas (9) to (14) used are chosen so that the desired organopolysiloxane particles are obtained.
  • the amounts of compounds of the general formulas (9) to (11) used are incorporated almost quantitatively in the first reaction step and control the degree of crosslinking of the organopolysiloxane particles in aqueous suspension.
  • the compounds of the general formulas (12) or (13) and (14) used in the second and, if appropriate, in the third reaction step are each used in excess and are therefore not completely incorporated into the organopolysiloxane particles.
  • the ratio of the amount of the compounds of the general formula (12) used in the second reaction step to the amount of the compound of the general formula (13) and (14) used in the third reaction step is preferably 1:10 to 2: 1, in particular 1: 5 to 1: 1.
  • Aliphatically substituted benzenesulfonic acids and their salts and optionally partially ethoxylated quaternary ammonium halides and hydroxides are preferred.
  • Dodecylbenzenesulfonic acid and benzyldimethyl- (2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy] ethyl ⁇ ammonium chloride (benzethonium chloride) are particularly preferred.
  • the amount of emulsifier to be used is from 0.5 to 50% by weight, preferably from 1.0 to 30% by weight, in each case based on the total amount of organosilicon starting compounds used in the first and second reaction steps.
  • the organosilicon starting compounds of the general formulas (9) to (11) are preferably metered in during the first reaction step.
  • All starting components of the general formulas (9) are preferably to (11) mixed in the desired ratio before metering during the first reaction step;
  • an additional 0.1-30% by weight, based on the sum of the starting components of the general formulas (9) to (11), alkanol of the formula R 7 OH, in which R 7 is an alkyl radical, is optionally added 1 to 5 carbon atoms is added as a solubilizer, with the alkanols methanol and ethanol being particularly preferred.
  • the above-described ethers, hydrocarbons, ketones and organopolysiloxanes, in particular tetrahydrofuran, cyclohexane, methylcyclohexane or toluene, are preferably used as the aprotic organic solvent.
  • the reaction both in the first (emulsion polycondensation / polymerization) and in the second reaction step is preferably carried out at 5-95 ° C., in particular at 10-85 ° C. and particularly preferably at 10-40 ° C.
  • the pH is in each case from 1 to 12, preferably from 1 to 4 or from 7 to 11, depending on the acid / base stability of the radicals R , R 4 , R 5 and R 6 of the starting compounds (9) to (13) .
  • the stability of the emulsion in the preparation of the colloidal suspensions during the first reaction step, it is advantageous for the stability of the emulsion to stir for a further 1 to 24 hours after the end of the metering of the organosilicon starting compounds of the general formulas (9) to (11).
  • the alkanol released during the hydrolysis can be removed by distillation, if appropriate under reduced pressure, but this is not preferred.
  • the solids content of the colloidal suspension produced after the first step should preferably be at most 25% by weight, since otherwise a high increase in viscosity makes further implementation difficult.
  • the reaction with organosilicon compound of the general formulas (13) and (14) in the third reaction step is preferably carried out at 5-95 ° C., in particular at 10-85 ° C. and particularly preferably at 10-40 ° C. To achieve the most complete possible reaction, it is again advantageous to stir for a further 1-24 hours after the addition of the compound of the general formulas (13) and (14) has ended.
  • Static and dynamic light scattering is particularly suitable for the structural characterization of the organopolysiloxane particles.
  • Static and dynamic light scattering are established methods known to those skilled in the art in macromolecular chemistry and colloid chemistry for characterizing disperse particles.
  • Static light scattering averages the scattering intensity at different angles over a sufficiently long time interval and provides information about the static properties of the macromolecules, such as the weight-average molecular weight M w , the z-mean of the square of the radius of inertia ⁇ R g 2 ⁇ z , and the second virial coefficient A 2 , which describes the intra- and intermolecular thermodynamic interactions of the dispersed particles with the solvent.
  • the particle shape can be determined from the angle dependence of the scattered light and any existing structuring in solution can be clarified.
  • the simultaneous static and dynamic light scattering measurement makes it possible to make the above statements about the system under investigation with a single experiment and thus obtain information e.g. to get about particle size, dispersion, and shape, as well as molecular weight and density.
  • M. Schmidt Simultaneous Static and Dynamic Light Scattering: Applications to Polymer Structure Analysis, in: Dynamic Light Scattering: The Method and some Applications; Brown, W. (ed.); Oxford University Press, Oxford, UK, 372-406 (1993).
  • the quotient of the inertia and hydrodynamic radius provides structural information about the particle shape, such as a hard ball, hollow ball, ball, stick or star polymer.
  • the preferred organopolysiloxane particles are therefore spherical.
  • the size range of the organopolysiloxane particles represents the border area between large molecules, oligomers and dendrimers on the one hand and small solids on the other hand, thus corresponds to a seam between the solid and the molecule.
  • collective solid-state properties have not yet been developed; on the other hand, molecular behavior can no longer be observed or can only be observed to some extent. Examples of particulate structures of this size with an almost fixed conformation are microgels. According to Antonietti (Angew.
  • Type B microgels with particle diameters in the mesoscopic size range from 5 to 200 are obtained from aqueous colloidal systems nm and molecular weights from 10 6 to 10 11 (g / mol) referred to as "Type B" microgels.
  • "Type B" microgels are particularly interesting, for example as fillers or compatibilizers for (optically transparent) polymers or as potential starting materials for tailor-made catalyst systems.
  • the organopolysiloxane particles are particularly suitable as additives for polymer modification.
  • Soft elastic particles can be used as impact modifiers, hard particles as fillers.
  • reactive groups such as vinyl, allyl or methacrylate
  • the organopolysiloxane particles can be used as reactive fillers or reactive modifiers, which are chemically bound to the matrix and have a strong influence on the mechanical properties of the surrounding polymer matrix.
  • particulate graft copolymers can be built up specifically from siloxane core and organopolymer shell.
  • Hydridofunctional organopolysiloxane particles can be converted and further functionalized almost arbitrarily by subsequent hydrosilylation reactions; alternatively, just like vinyl- or allyl-functional organopolysiloxane particles, they can be used as crosslinking, reinforcing or elastic particles in hydrosilylation reactions.
  • Static and dynamic light scattering were measured with a system that u. a. Consists of a Stabilite TM 2060-lls Kr laser from Spectra-Physics, a goniometer Sp-86 from ALV and an ALV-3000 digital structure / correlator. The krypton ion laser worked with a wavelength of 647.1 nm.
  • Sample preparation The samples (organopolysiloxane particles in toluene; the respective concentration range is given in the examples) were filtered three times through Millex TM -FGS filters (0.2 ⁇ m pore size) from Millipore.
  • the measurement temperature in the light scattering experiments was 20 ° C.
  • the dynamic light scattering measurements were carried out in 20 ° steps, depending on the angle from 50 ° to 130 °, the correlation functions were evaluated with the simplex algorithm. In the static light scattering experiment, the angle dependence of the scattered light from 30 ° to 140 ° was measured in 5 ° steps.
  • the molecular weight M w of the monodisperse, spherical particles was found to be 2.0x10 6 .
  • the organopolysiloxane particles are readily soluble in toluene, pentane, cyclohexane, dimethylformamide, tetrahydrofuran, dioxane, diethyl ether, methyl methacrylate, styrene and poly (dimethylsiloxane) with a viscosity of 35 mPa ⁇ s.
  • a mixture of 13.3 g of methyltrimethoxysilane and 11.7 g of dimethyldimethoxysilane was metered into a template from 125 g of water, 3 g of benzethonium chloride and 0.3 g of sodium hydroxide solution (10% in water) over the course of 1 hour with stirring. After stirring for a further 10 hours, 25 g of the resulting suspension were mixed with stirring with 1.2 g of trimethylmethoxysilane and stirred for a further 10 hours. The suspension was broken by adding 50 ml of methanol. The precipitated solid was filtered off, washed 3 times with 30 ml of methanol and taken up in 50 ml of toluene.
  • the molecular weight M w of the monodisperse, spherical particles was found to be 2.0x10 6 .
  • the organopolysiloxane particles are readily soluble in toluene, tetrahydrofuran, chloroform, cyclohexane, pentane and methyl methacrylate.
  • a mixture of 8.2 g of methyltrimethoxysilane and 16.8 g of dimethyldimethoxysilane was metered into a template from 125 g of water, 3 g of benzethonium chloride and 0.3 g of sodium hydroxide solution (10% strength in water) over the course of 1 hour with stirring.
  • the procedure was as in Example 2. There were 1.7 g of a white powder which is composed of [(CH 3 ) 3 SiO 1/2 ], [(CH 3 ) 2 SiO 2/2 ] and [CH 3 SiO 3/2 ] units , receive.
  • a hydrodynamic particle radius R h of 17.3 nm and an inertia radius R g of 13.7 nm were determined by means of static and dynamic light scattering (solvent toluene; concentration range of the measurement: 0.05-2 g / l). This results in a ⁇ ratio of 0.79.
  • the molecular weight M w of the monodisperse, spherical particles was found to be 5.13x10 6 .
  • the poly (organosiloxane) particles are readily soluble in toluene, tetrahydrofuran, chloroform, cyclohexane, pentane and methyl methacrylate.
  • a mixture of 2.8 g of methyltrimethoxysilane and 22.2 g of dimethyldimethoxysilane was metered into a template from 125 g of water, 3 g of benzethonium chloride and 0.3 g of sodium hydroxide solution (10% in water) over the course of 1 hour with stirring. 25 g of the resulting suspension were mixed with 1.0 g of trimethylmethoxysilane while stirring and stirred for a further 48 hours. The addition of 50 ml of methanol Suspension broken. The precipitated solid was filtered off, washed 3 times with 30 ml of methanol and taken up in a little toluene.
  • a mixture of 1.4 g of methyltrimethoxysilane and 23.6 g of dimethyldimethoxysilane was metered into a template from 125 g of water, 3 g of benzethonium chloride and 0.3 g of sodium hydroxide solution (10% strength in water) over the course of 1 hour with stirring.
  • the procedure was as in Example 4.
  • 1.8 g of a white, rubber-elastic powder which consisted of [(CH 3 ) 3 SiO 1/2 ], [(CH 3 ) 2 SiO 2/2 ] and [CH 3 SiO 3/2 ] units were obtained is built up.
  • a hydrodynamic particle radius R h of 32.0 nm and an inertia radius R g of 28.5 nm were determined by means of static and dynamic light scattering (solvent toluene; concentration range of the measurement: 0.05-2 g / l). This results in a ⁇ ratio of 0.85.
  • the molecular weight M w of the monodisperse, spherical particles was determined to be 6.50x10 6 .
  • the organopolysiloxane particles are readily soluble in toluene, tetrahydrofuran, chloroform, cyclohexane and pentane.
  • a hydrodynamic particle radius R h of 11.9 nm and an inertia radius R g of 10 nm were determined using static and dynamic light scattering (solvent toluene; concentration range of the measurement: 1.0-2.5 g / l). This results in a ⁇ ratio of 0.84.
  • the molecular weight M w of the monodisperse, spherical particles was found to be 2.0x10 6 .
  • the organopolysiloxane particles are readily soluble in toluene, pentane, cyclohexane, dimethylformamide, tetrahydrofuran, dioxane, diethyl ether, methyl methacrylate, styrene and poly (dimethylsiloxane) with a viscosity of 35 mPa ⁇ s.
  • a hydrodynamic particle radius R h of 9.5 nm and an inertia radius R g of ⁇ 10 nm were determined using static and dynamic light scattering (solvent toluene; concentration range of the measurement: 1.0 - 3.0 g / l). This results in a ⁇ ratio of ⁇ 1.0.
  • the molecular weight M w of the monodisperse, spherical particles was found to be 1.6x10 6 .
  • the incorporation of the Si-H functions was qualitatively determined by IR spectroscopy (KBr compact, ⁇ Si-H 2238 cm -1 ) and by 1 H-NMR spectroscopy (CDCl 3 , ⁇ Si-H 4.0-5, 5 ppm).
  • the organopolysiloxane particles are readily soluble in toluene, pentane, cyclohexane, tetrahydrofuran, dioxane, diethyl ether and poly (dimethylsiloxane) with a viscosity of 35 mPa ⁇ s.
  • the molecular weight M w of the monodisperse, spherical particles was found to be 0.86x10 6 .
  • the incorporation of the azo-functional silane was verified qualitatively and quantitatively by DSC measurements.
  • the organopolysiloxane particles are readily soluble in toluene, pentane, cyclohexane, tetrahydrofuran, dioxane and methyl methacrylate.
  • Example 2 Analogously to Example 1, 25.0 g of methyltrimethoxysilane were metered in over the course of 45 minutes to a template from 125 g of water, 3 g of benzethonium chloride and 0.3 g of sodium hydroxide solution (10% in water). After stirring for a further 5 hours, 25 g of the resulting suspension were broken by adding 50 ml of methanol. The precipitated solid was filtered off and washed 3 times with 30 ml of methanol. It proved to be insoluble in toluene and could not be further implemented and characterized.
  • a mixture of 19.5 g of methyltrimethoxysilane and 5.5 g of trimethylmethoxysilane was metered into a template from 125 g of water, 3 g of benzethonium chloride and 0.3 g of sodium hydroxide solution (10% strength in water) over the course of 60 minutes. After stirring for a further 10 hours, 25 g of the resulting suspension were broken by adding 50 ml of methanol. The precipitated solid was filtered off and washed 3 times with 30 ml of methanol. It proved to be insoluble in toluene and could not be further implemented and characterized.
  • a mixture of 14.0 g of methyltrimethoxysilane and 11.0 g of trimethylmethoxysilane was metered into a template from 125 g of water, 3 g of benzethonium chloride and 0.3 g of sodium hydroxide solution (10% strength in water) over the course of 90 minutes. After stirring for a further 15 hours, 25 g of the resulting suspension were broken by adding 50 ml of methanol. A highly viscous oil was obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
EP96108218A 1995-05-26 1996-05-23 Particules solubles monodispersées d'organopolysiloxane Expired - Lifetime EP0744432B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19519446 1995-05-26
DE19519446A DE19519446A1 (de) 1995-05-26 1995-05-26 Monodisperse lösliche Organopolysiloxanpartikel

Publications (2)

Publication Number Publication Date
EP0744432A1 true EP0744432A1 (fr) 1996-11-27
EP0744432B1 EP0744432B1 (fr) 1999-01-13

Family

ID=7763002

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96108218A Expired - Lifetime EP0744432B1 (fr) 1995-05-26 1996-05-23 Particules solubles monodispersées d'organopolysiloxane

Country Status (9)

Country Link
US (1) US5854369A (fr)
EP (1) EP0744432B1 (fr)
JP (1) JP2758388B2 (fr)
KR (1) KR100197343B1 (fr)
CN (1) CN1073586C (fr)
AT (1) ATE175696T1 (fr)
DE (2) DE19519446A1 (fr)
ES (1) ES2128808T3 (fr)
TW (1) TW457260B (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011984A1 (fr) * 1995-09-28 1997-04-03 Wacker-Chemie Gmbh Particules d'organopolysiloxane mesoscopiques presentant des composes metalliques chimiquement lies
EP0857748A1 (fr) * 1997-02-06 1998-08-12 Wacker-Chemie GmbH Dépots métalliques sur des particules d'organopolysiloxane
EP0852244A3 (fr) * 1997-01-03 1998-12-02 General Electric Company Méthode pour la préparation des dispersions aqueuse et structurées de polysiloxane
EP1006147A1 (fr) * 1998-12-04 2000-06-07 Wacker-Chemie GmbH Compositions de polysiloxane à composant unique durcissables par la chaleur et par addition
US6099964A (en) * 1997-02-06 2000-08-08 Wacker-Chemie Gmbh Metal deposits on mesoscopic organopolysiloxane particles
DE19904816A1 (de) * 1999-02-05 2000-09-14 Espe Dental Ag Dentalwerkstoff und Verwendung von monodispersen Organopolysiloxanpartikeln als Inhaltsstoff in einem Dentalwerkstoff
US6358876B1 (en) 1997-09-18 2002-03-19 Wacker-Chemie Gmbh Organo-aluminum compounds immobilized on organopolysiloxane microgel particles
WO2002055587A1 (fr) * 2001-01-09 2002-07-18 Queen Mary & Westfield College Organopolysiloxanes contenant des groupes phosphoniques, methodes de production et d'utilisation de ces composes
US6541412B1 (en) 1999-12-10 2003-04-01 Univation Technologies, Llc Catalyst system method for preparing and using same in a polymerization process
CN100354354C (zh) * 2004-09-14 2007-12-12 瓦克化学股份公司 具有提高的防污性及提高的粘合性的聚硅氧烷面漆
DE102007024967A1 (de) 2007-05-30 2008-12-04 Wacker Chemie Ag Kern-Schalepartikel enthaltende Reaktionsharze und Verfahren zu ihrer Herstellung und deren Verwendung
EP2067811A1 (fr) 2007-12-06 2009-06-10 Evonik Goldschmidt GmbH Particules de silicone (méth-)acrylate, leurs procédé de fabrication et d'utilisation
DE102008044199A1 (de) 2008-11-28 2010-06-02 Wacker Chemie Ag Siloxan-Mischungen enthaltende Epoxidharze und Verfahren zu ihrer Herstellung und deren Verwendung
US7816009B2 (en) 2003-04-07 2010-10-19 Wacker Chemie Ag Organosilyl functionalized particles and the production thereof
DE102010001528A1 (de) 2010-02-03 2011-08-04 Evonik Goldschmidt GmbH, 45127 Neue Partikel und Kompositpartikel, deren Verwendungen und ein neues Verfahren zu deren Herstellung aus Alkoxysilylgruppen tragenden Alkoxylierungsprodukten
EP2886102A1 (fr) 2013-12-19 2015-06-24 Evonik Industries AG Particules de silicone (méth-)acrylate, son procédé de fabrication et d'utilisation

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19816148A1 (de) * 1998-04-09 1999-10-21 Wacker Chemie Gmbh Organopolysiloxanpartikel enthaltende acrylathaltige Zusammensetzung
DE19934438B4 (de) * 1999-07-22 2008-01-17 Wacker Chemie Ag Verfahren zur Herstellung einer wässrigen 1-Komponenten Siliconzusammensetzung
US6624214B2 (en) 2000-03-10 2003-09-23 The Goodyear Tire & Rubber Company Rubber compositions containing preciptated organosilicon particles having a core and a shell
DE10032820A1 (de) * 2000-07-06 2002-01-24 Wacker Chemie Gmbh Verfahren zur Isolierung von Polyorganosiloxanen
DE102004047707A1 (de) * 2004-09-30 2006-04-06 Wacker Chemie Ag Organopolysiloxanpartikel enthaltende Zusammensetzung und deren Herstellung
EP2277939B1 (fr) 2005-03-24 2017-02-22 Bridgestone Corporation Compoundage d'une composition de caoutchouc renforcé à l'aide de silicium présentant un faible taux d'émission de VOC
US7915368B2 (en) 2007-05-23 2011-03-29 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes
US8501895B2 (en) 2007-05-23 2013-08-06 Bridgestone Corporation Method for making alkoxy-modified silsesquioxanes and amino alkoxy-modified silsesquioxanes
US8962746B2 (en) 2007-12-27 2015-02-24 Bridgestone Corporation Methods of making blocked-mercapto alkoxy-modified silsesquioxane compounds
US8097674B2 (en) 2007-12-31 2012-01-17 Bridgestone Corporation Amino alkoxy-modified silsesquioxanes in silica-filled rubber with low volatile organic chemical evolution
US8794282B2 (en) 2007-12-31 2014-08-05 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US8642691B2 (en) 2009-12-28 2014-02-04 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for improved metal adhesion and metal adhesion retention to cured rubber
US11401440B2 (en) 2014-12-31 2022-08-02 Bridgestone Corporation Amino alkoxy-modified silsesquioxane adhesives for adhering steel alloy to rubber
WO2020133158A1 (fr) * 2018-12-28 2020-07-02 湖州五爻硅基材料研究院有限公司 Procédé de préparation de poudre de silicone sphérique ou d'agglomérats associés et poudre de silicone sphérique ou agglomérats associés ainsi préparés
US11746174B2 (en) 2019-11-19 2023-09-05 Industrial Technology Research Institute Biodegradable polyester

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291939A2 (fr) * 1987-05-21 1988-11-23 Wacker-Chemie Gmbh Procédé de préparation de poudres de résine de silicone
EP0335414A2 (fr) * 1988-03-31 1989-10-04 Wacker-Chemie Gmbh Organosols d'organopolysiloxanes et leur procédé de préparation
FR2639950A1 (fr) * 1988-12-02 1990-06-08 Toshiba Silicone
JPH05148364A (ja) * 1991-11-26 1993-06-15 Shin Etsu Chem Co Ltd 球状シリコーン樹脂微粒子の製造方法
WO1993023455A1 (fr) * 1992-05-15 1993-11-25 Wacker-Chemie Gmbh Procede de fabrication de resine organopolysiloxanique
JPH06192426A (ja) * 1992-12-22 1994-07-12 Shin Etsu Chem Co Ltd 球状シリコーン樹脂微粒子の製造方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5148364A (ja) * 1974-10-24 1976-04-26 Victor Company Of Japan Jidoreberukiokuseigyosochi
US4424297A (en) * 1982-07-08 1984-01-03 Dow Corning Corporation Colloidal silesquioxanes
DE3226091C2 (de) * 1982-07-13 1986-11-20 Degussa Ag, 6000 Frankfurt Polymere Di-, Tri- oder Tetrasulfide, Verfahren zu ihrer Herstellung und Verwendung
JPH0629303B2 (ja) * 1984-05-30 1994-04-20 三菱レイヨン株式会社 ポリオルガノシロキサン系グラフト共重合体の製造法
JPS6192436A (ja) * 1984-10-11 1986-05-10 Hitachi Ltd 光デイスク装置
JPH01185367A (ja) * 1988-01-18 1989-07-24 Toshiba Silicone Co Ltd 表面処理されたポリメチルシルセスキオキサン粉末の製造方法
US5250615A (en) * 1988-10-31 1993-10-05 Japan Synthetic Rubber Co., Ltd. Polyorganosiloxane series thermoplastic resin and composition thereof
JP3382939B2 (ja) * 1990-12-28 2003-03-04 三菱レイヨン株式会社 透明性に優れた鋳込み重合物およびその製法
US5385988A (en) * 1991-09-24 1995-01-31 Mitsubishi Rayon Co., Ltd. Composite composition having high transparency and process for producing same
US5319040A (en) * 1993-03-12 1994-06-07 General Electric Company Method for making substantially silanol-free silicone resin powder, product and use

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291939A2 (fr) * 1987-05-21 1988-11-23 Wacker-Chemie Gmbh Procédé de préparation de poudres de résine de silicone
EP0335414A2 (fr) * 1988-03-31 1989-10-04 Wacker-Chemie Gmbh Organosols d'organopolysiloxanes et leur procédé de préparation
FR2639950A1 (fr) * 1988-12-02 1990-06-08 Toshiba Silicone
JPH05148364A (ja) * 1991-11-26 1993-06-15 Shin Etsu Chem Co Ltd 球状シリコーン樹脂微粒子の製造方法
WO1993023455A1 (fr) * 1992-05-15 1993-11-25 Wacker-Chemie Gmbh Procede de fabrication de resine organopolysiloxanique
JPH06192426A (ja) * 1992-12-22 1994-07-12 Shin Etsu Chem Co Ltd 球状シリコーン樹脂微粒子の製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 93-224366, XP002011996 *
DATABASE WPI Derwent World Patents Index; AN 94-260609, XP002011997 *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6008309A (en) * 1995-09-28 1999-12-28 Wacker-Chemie Gmbh Mesoscopic organopolysiloxane particles with chemically bound metallic compounds
WO1997011984A1 (fr) * 1995-09-28 1997-04-03 Wacker-Chemie Gmbh Particules d'organopolysiloxane mesoscopiques presentant des composes metalliques chimiquement lies
EP0852244A3 (fr) * 1997-01-03 1998-12-02 General Electric Company Méthode pour la préparation des dispersions aqueuse et structurées de polysiloxane
US5900460A (en) * 1997-01-03 1999-05-04 General Electric Company Process for the synthesis of structured aqueous dispersions of polysiloxanes
EP0857748A1 (fr) * 1997-02-06 1998-08-12 Wacker-Chemie GmbH Dépots métalliques sur des particules d'organopolysiloxane
US6099964A (en) * 1997-02-06 2000-08-08 Wacker-Chemie Gmbh Metal deposits on mesoscopic organopolysiloxane particles
US6358876B1 (en) 1997-09-18 2002-03-19 Wacker-Chemie Gmbh Organo-aluminum compounds immobilized on organopolysiloxane microgel particles
EP1006147A1 (fr) * 1998-12-04 2000-06-07 Wacker-Chemie GmbH Compositions de polysiloxane à composant unique durcissables par la chaleur et par addition
US6251969B1 (en) 1998-12-04 2001-06-26 Wacker-Chemie Gmbh Thermocurable, one-component, addition-crosslinking silicone compositions
DE19904816A1 (de) * 1999-02-05 2000-09-14 Espe Dental Ag Dentalwerkstoff und Verwendung von monodispersen Organopolysiloxanpartikeln als Inhaltsstoff in einem Dentalwerkstoff
US6541412B1 (en) 1999-12-10 2003-04-01 Univation Technologies, Llc Catalyst system method for preparing and using same in a polymerization process
US7064226B2 (en) 2001-01-09 2006-06-20 Phosphonics Limited Organopolysiloxanes containing phosphonic groups, method for the production and use thereof
WO2002055587A1 (fr) * 2001-01-09 2002-07-18 Queen Mary & Westfield College Organopolysiloxanes contenant des groupes phosphoniques, methodes de production et d'utilisation de ces composes
US7816009B2 (en) 2003-04-07 2010-10-19 Wacker Chemie Ag Organosilyl functionalized particles and the production thereof
CN100354354C (zh) * 2004-09-14 2007-12-12 瓦克化学股份公司 具有提高的防污性及提高的粘合性的聚硅氧烷面漆
DE102007024967A1 (de) 2007-05-30 2008-12-04 Wacker Chemie Ag Kern-Schalepartikel enthaltende Reaktionsharze und Verfahren zu ihrer Herstellung und deren Verwendung
EP2067811A1 (fr) 2007-12-06 2009-06-10 Evonik Goldschmidt GmbH Particules de silicone (méth-)acrylate, leurs procédé de fabrication et d'utilisation
DE102007058713A1 (de) 2007-12-06 2009-06-10 Evonik Goldschmidt Gmbh Silicon(meth-)acrylat-Partikel, Verfahren zu deren Herstellung sowie deren Verwendung
DE102008044199A1 (de) 2008-11-28 2010-06-02 Wacker Chemie Ag Siloxan-Mischungen enthaltende Epoxidharze und Verfahren zu ihrer Herstellung und deren Verwendung
US8507618B2 (en) 2008-11-28 2013-08-13 Wacker Chemie Ag Siloxane mixtures containing epoxide resins and method for the preparation thereof and use thereof
DE102010001528A1 (de) 2010-02-03 2011-08-04 Evonik Goldschmidt GmbH, 45127 Neue Partikel und Kompositpartikel, deren Verwendungen und ein neues Verfahren zu deren Herstellung aus Alkoxysilylgruppen tragenden Alkoxylierungsprodukten
EP2354177A1 (fr) 2010-02-03 2011-08-10 Evonik Goldschmidt GmbH Particules et particules composites, leurs utilisations et un procédé destiné à leur fabrication à partir de produits d'alkoxylation portant des groupes alkoxysilyles
EP2886102A1 (fr) 2013-12-19 2015-06-24 Evonik Industries AG Particules de silicone (méth-)acrylate, son procédé de fabrication et d'utilisation
DE102013226568A1 (de) 2013-12-19 2015-06-25 Evonik Industries Ag Silicon(meth-)acrylat-Partikel, Verfahren zu deren Herstellung sowie deren Verwendung
US9725538B2 (en) 2013-12-19 2017-08-08 Evonik Degussa Gmbh Silicone (meth)acrylate particles, processes for their preparation and use thereof

Also Published As

Publication number Publication date
JP2758388B2 (ja) 1998-05-28
KR960041236A (ko) 1996-12-19
CN1073586C (zh) 2001-10-24
EP0744432B1 (fr) 1999-01-13
JPH08319350A (ja) 1996-12-03
TW457260B (en) 2001-10-01
KR100197343B1 (ko) 1999-06-15
US5854369A (en) 1998-12-29
CN1137046A (zh) 1996-12-04
DE59601131D1 (de) 1999-02-25
ATE175696T1 (de) 1999-01-15
DE19519446A1 (de) 1996-11-28
ES2128808T3 (es) 1999-05-16

Similar Documents

Publication Publication Date Title
EP0744432B1 (fr) Particules solubles monodispersées d'organopolysiloxane
EP0659838B1 (fr) Copolymeres d'organopolysiloxane comme macro-initiateur radicalaire
DE69021351T2 (de) Teilchen mit einem Siliziumdioxidkern und eine Silikonschale, diese enthaltende darin dispergierte Emulsion und Verfahren zur Herstellung dieser Emulsion.
DE69723752T2 (de) Silikonkautschukpulver und Verfahren zur Herstellung
DE69825521T2 (de) Verfahren zur Herstellung von Silicon-in-Wasser-Emulsionen
DE3784447T2 (de) Haertbare organopolysiloxanzusammensetzung.
DE69423319T2 (de) Mit Polysiloxanharz beschichtete Siloxankautschukpartikel
DE60312194T2 (de) Silikonelastomerzusammensetzungen
DE69919091T2 (de) Emulsion mit Riechstoff freigebendem Siliziumverbindungen
DE3854715T2 (de) Verfahren zur Herstellung von wässrigen Zusammensetzungen auf Basis von Siliconen und organischen Polymeren.
EP1721926B1 (fr) Procédé pour la fabrication de dispersions à base d'organopolysiloxanes réticulés
DE102005039398A1 (de) Verfahren zur Herstellung von Anlagerungsprodukten aus SiH-Gruppen enthaltenden Verbindungen an Olefingruppen aufweisende Reaktionspartner in wässrigen Medien
DE3786868T2 (de) Beschichtungszusammensetzung auf der Basis eines hitzehärtenden Fluorosiloxans.
EP1690884B1 (fr) Polysiloxanes modifiés par de l'organosilane et leur utilisation pour la modification de surfaces
DE102007020568A1 (de) Verfahren zur kontinuierlichen Herstellung von Aminoalkylgruppen aufweisenden Organopolysiloxanen
DE69619042T2 (de) Mikropartikelkatalysatoren für Hydrosilylierungsreaktionen und hitzehärtbare Silikonzusammensetzungen die diesen Katalysator enthalten
DE69606925T2 (de) Lösungsmittelfreie Silikonharze
DE69918645T2 (de) Verfahren zur Herstellung von Siloxan-Oxyalkylen-Copolymeren
CN102197093B (zh) 从分散体形成的金属化的颗粒
JP7426283B2 (ja) ポリエーテル／ポリシロキサン架橋ゴム球状粒子及びこれを製造する方法、並びにポリエーテル／ポリシロキサン架橋複合粒子及びこれを製造する方法
EP0659805B1 (fr) Macroinitiateurs radicalaires à base de polysiloxanes solubles pour la copolymérisation par greffage
EP0852595A1 (fr) Particules d'organopolysiloxane mesoscopiques presentant des composes metalliques chimiquement lies
EP4077491B1 (fr) Particules de silicone à noyau réticulé et préparation correspondante
CN107558238B (zh) 包含含有氨基烷基和聚氧化亚烷基的硅氧烷的乳液组合物
DE69119868T2 (de) Verfahren zur Herstellung von Organopolysiloxanen mit einem kontrollierten und niedrigen Gehalt an Hydroxylgruppen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19960523

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB IT LI NL

17Q First examination report despatched

Effective date: 19961227

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB IT LI NL

REF Corresponds to:

Ref document number: 175696

Country of ref document: AT

Date of ref document: 19990115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 59601131

Country of ref document: DE

Date of ref document: 19990225

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19990210

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2128808

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20070502

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20070524

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20070528

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20070530

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20070615

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20070702

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20070525

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20070525

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20070517

Year of fee payment: 12

BERE Be: lapsed

Owner name: *WACKER-CHEMIE G.M.B.H.

Effective date: 20080531

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20080523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081201

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080523

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20090119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080602

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080523

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20080524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080524